Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides

ABSTRACT

Provided herein are methods for preparing vinylidene-terminated polyolefins. Further, provided herein are novel sulfide-terminated polyolefins of the formula: 
                         
wherein R 1  is a polyolefin group and R 2  is hydrocarbyl; and methods for producing the same.

This application is a divisional application of U.S. patent applicationSer. No. 12/256,441, which was filed Oct. 22, 2008, the entirety ofwhich is incorporated by reference herein.

1. FIELD

Provided herein are methods for producing vinylidene-terminatedpolyolefins. Further, provided herein are novel sulfide-terminatedpolyolefins and methods for producing the same.

2. BACKGROUND

Terminally functionalized polymers are useful precursors for thepreparation of polymers containing functional end groups. Examples ofterminally functionalized polymers are vinylidene-terminatedpolyolefins. Polymers containing functional end groups have severaluseful purposes. For example, polyisobutylene (PIB) containingvinylidene chain ends are utilized in the synthesis of PIB-succinicanhydrides (PIBSAs), which are key intermediates in the production ofPIB-based succinimide dispersants for use as additives for enginelubricants. Vinylidene-terminated PIBs are also utilized in theproduction of PIB-amines, which are useful as fuel additives. Anopportunity exists to create polyolefins containing sulfide end groupsfor use in lubricant applications. These thio-terminated polyolefins canoffer oxidation inhibition and surface affinity, two important factorsin the design of lubricant additive technology. Thus, there is a needfor new classes of terminally functionalized polymers, as well asmethods of selectively or exclusively producing terminallyfunctionalized polymers, such as vinylidene-terminate polyolefins andsulfide-terminated polyolefins.

3. SUMMARY

In some embodiments, provided herein are methods for preparingtelechelic polyolefins, comprising:

-   -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin from step (a) with one or        more disulfides to form an intermediate; and    -   c. reacting the intermediate of step (b) with one or more        alcohols, amines, or thiols.

In some embodiments, provided herein are methods for preparing avinylidene terminated polyolefin, comprising:

-   -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin from step (a) with one or        more disulfides to form an intermediate; and    -   c. reacting the intermediate of step (b) with one or more        alcohols or amines.

In some embodiments, provided herein are methods for preparing acompound of the formula:

or a mixture thereof;

-   -   wherein R¹ is a polyolefin group;        -   R^(A) and R^(B) are each, independently, alkyl, aryl,            aralkyl, alkaryl,

-   -   -   wherein m is 1-3; n is 1-3; p is 1-3;            -   X is halo or a pseudohalide;            -   R^(x) is alkyl or aryl;            -   R³ is tert-butyl; and            -   R⁴ and R⁵ are each, independently, alkyl, aryl, aralkyl,                or alkaryl; comprising:

    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;

    -   b. reacting the ionized polyolefin from step (a) with one or        more compounds of the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate; and

    -   c. reacting the intermediate of step (b) with one or more        alcohols, amines, or thiols.

In some embodiments, provided herein are methods for preparing acompound of the formula:

wherein R¹ is a polyolefin group; and

-   -   R^(C) is alkyl, aryl, aralkyl, alkaryl, substituted alkyl, or        substituted aryl; comprising:    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin with one or more compounds of        the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate;        -   wherein R^(A) and R^(B) are each, independently, alkyl,            aryl, aralkyl, or alkaryl; and    -   c. reacting the intermediate from step (b) with one or more        compounds of the formula:        R^(C)—SH.

In some embodiments, provided herein are compounds of the formula:

wherein R¹ is a polyolefin group;

and R^(D) is alkyl of 1 to 7 carbons, substituted alkyl of at least 3carbons, unsubstituted aryl, alkaryl, aralkyl,

wherein m is 1-3; n is 1-3; p is 1-3;

-   -   X is halo or a pseudohalide;    -   R³ is tert-butyl;    -   R⁴ and R⁵ are each, independently, aryl or alkyl; and    -   R^(x) is hydrocarbyl.

Without being limited to any theory, in some embodiments, the methodsdescribed herein proceed by the pathway shown in the following scheme:

wherein

R¹ is a polyolefin group;

R² is hydrocarbyl or hydrogen;

R^(A), R^(B), and R^(C) are each, independently, hydrocarbyl orsubstituted hydrocarbyl;

M is a metal, transition metal, or metalloid;

Y is independently halo or alkyl; and

α and β are each, independently, an integer from 1 to 20.

4. DETAILED DESCRIPTION 4.1 Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of ordinary skillin the art. In the event that there are a plurality of definitions for aterm used herein, the definitions provided in this section prevailunless stated otherwise.

As used herein, “alcohol” refers to a compound of the following formula:R—OH;wherein R is hydrocarbyl or substituted hydrocarbyl. In someembodiments, the hydrocarbyl is aliphatic. In some embodiments, R isalkyl or substituted alkyl. In some embodiments, the —OH is attached toa primary carbon. In some embodiments, the —OH is attached to asecondary carbon. In some embodiments, the —OH is attached to a tertiarycarbon. In some embodiments, the alcohol contains more than one hydroxylgroup. In some embodiments, the alcohol contains one hydroxyl group.

As used herein, “alkane” refers to a hydrocarbon containing only singlebonds. In some embodiments, the alkane contains a straight hydrocarbonchain. In some embodiments, the alkane contains a branched hydrocarbonchain. In some embodiments, the alkane is cyclic. In some embodiment,the alkane contains 1 to 10 carbons. In some embodiment, the alkanecontains 1 to 8 carbons. In some embodiment, the alkane contains 1 to 6carbons. In some embodiment, the alkane contains 1 to 3 carbons. In someembodiment, the alkane contains 1 to 2 carbons. In some embodiments, thealkane contains 5 to 6 carbons. In some embodiments, the alkane ispentane. In some embodiments, the alkane is hexane. In some embodiments,the alkane is substituted.

As used herein, “alkaryl” refers to an aryl group substituted with atleast one alkyl, alkenyl, or alkynyl group.

As used herein, “alkenyl” refers to a hydrocarbon chain or group ofabout 2 to about 20 carbons, wherein the chain or group contains one ormore double bonds. In some embodiments, the alkenyl contains about 2 toabout 15 carbons. In some embodiments, the alkenyl contains about 2 toabout 10 carbons. In some embodiments, the alkenyl contains about 2 toabout 8 carbons. In some embodiments, the alkenyl contains about 2 toabout 6 carbons. In some embodiments, the alkenyl contains about 2 toabout 3 carbons. In some embodiments, the alkenyl is an allyl group. Insome embodiments, the alkenyl group contains one or more double bondsthat are conjugated to another unsaturated group. In some embodiments,the alkenyl is substituted.

As used herein, “alkyl” refers to a hydrocarbon chain or group of about1 to about 20 carbons. In some embodiments, the alkyl contains about 1to about 15 carbons. In some embodiments, the alkyl contains about 1 toabout 10 carbons. In some embodiments, the alkyl contains about 1 toabout 8 carbons. In some embodiments, the alkyl contains about 1 toabout 6 carbons. In some embodiments, the alkyl contains about 1 toabout 3 carbons. In some embodiments, the alkyl contains 1 to 2 carbons.In some embodiments, the alkyl is primary. In some embodiments, thealkyl is secondary. In some embodiments, the alkyl is tertiary. In someembodiments, the alkyl is methyl, ethyl, n-propyl, isopropyl, isobutyl,n-butyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, orisohexyl. In some embodiments, the alkyl is methyl, ethyl, n-propyl, orisopropyl. In some embodiments, the alkyl is methyl. In someembodiments, the alkyl is tert-butyl. In some embodiments, the alkyl isa straight hydrocarbon chain. In some embodiments, the alkyl is abranched hydrocarbon chain. In some embodiments, the alkyl is cyclic. Insome embodiments, the alkyl is substituted.

As used herein, “alkynyl” refers to a hydrocarbon chain or group ofabout 2 to about 20 carbons, wherein the chain contains one or moretriple bonds. In some embodiments, the alkynyl contains about 2 to about15 carbons. In some embodiments, the alkynyl contains about 2 to about10 carbons. In some embodiments, the alkynyl contains about 2 to about 8carbons. In some embodiments, the alkynyl contains about 2 to about 6carbons. In some embodiments, the alkynyl contains about 2 to about 3carbons. In some embodiments, the alkynyl is a propargyl group. In someembodiments, the alkynyl group contains one or more triple bonds thatare conjugated to another unsaturated group. In some embodiments, thealkynyl is substituted.

As used herein, “amide” refers to a compound of the following formula:

wherein R¹-R³ are each, independently, hydrogen or optionallysubstituted hydrocarbyl. In some embodiments, R¹ is hydrogen. In someembodiments, R¹ is hydrocarbyl. In some embodiments, R² is hydrogen. Insome embodiments, R² and R³ are hydrocarbyl. In some embodiments, theamide is N,N-dimethylformamide.

As used herein, “amine” refers to a compound of the following formula:

wherein R¹, R², and R³ are each, independently, hydrogen or optionallysubstituted hydrocarbyl. In some embodiments, R¹, R², and R³ are each,independently, hydrogen or alkyl. In some embodiments, the amine is aprimary amine. In some embodiments, the amine is a secondary amine. Insome embodiments, the amine is a tertiary amine. In some embodiments,the amine is ammonia.

As used herein, “aralkyl” refers to an alkyl, alkenyl, or alkynyl groupsubstituted with at least one aryl group.

As used herein, “aryl” refers to a monocyclic or multicyclic aromaticgroup containing from 6 to about 30 cyclic carbons. In some embodiments,the aryl is monocyclic. In some embodiments, the aryl contains about 6to about 15 cyclic carbons. In some embodiments, the aryl contains about6 to about 10 cyclic carbons. In some embodiments, the aryl isfluorenyl, phenyl, or naphtyl. In some embodiments, the aryl is phenyl.In some embodiments, the aryl is a substituted aryl. The substitutedaryl is a substituted with a hydrocarbyl or a heteroatomic group,including, but not limited thios, thioethers, and halides.

As used herein, “binifer” refers to an inifer that is capable ofinitiation and propagation at two separate sites of an inifer. In someembodiments, the initiation and propagation occur simultaneously ornearly simultaneously at the two sites.

As used herein, “carbocation terminated polyolefin” refers to apolyolefin containing at least one carbocation end group. Examplesinclude, but are not limited to, compounds of the formula:

wherein R is a polyolefin group.

As used herein, “chain-end concentration” refers to the sum of the molarconcentration of carbocationic end groups and dormant end groups. When amono-functional initiator is used, the chain-end concentration isapproximately equal to the initiator concentration. For amulti-functional initiator, when the functionality of the initiatorequals x, then the chain end concentration is approximately equal to xtimes the initiator concentration.

As used herein, “common ion salt” refers to an ionic salt that isoptionally added to a reaction performed under quasiliving carbocationicpolymerization conditions to prevent dissociation of the propagatingcarbenium ion and counter-ion pairs.

As used herein, “common ion salt precursor” refers to an ionic salt thatis optionally added to a reaction performed under quasilivingcarbocationic polymerization conditions, wherein the ionic saltgenerates counter-anions that are identical to those of the propagatingchain ends, via in situ reaction with a Lewis acid.

As used herein, “diluent” refers to a liquid diluting agent or compound.Diluents may be a single or a mixture of two or more compounds oragents. Diluents may completely dissolve or partially dissolve thereaction components.

As used herein, “disulfide” refers to a compound of the followingformula:R¹—S—S—R²;wherein R¹ and R² are each, independently, optionally substitutedhydrocarbyl.

As used herein, “electron donor” refers to a molecule that is capable ofdonating a pair of electrons to another molecule.

As used herein, “halo” refers to halogen. In some embodiments, halo isF, Cl, Br, or I. In some embodiments, halo is F. In some embodiments,halo is Cl. In some embodiments, halo is Br. In some embodiments, halois I.

As used herein, heteroaryl refers to a monocyclic or multicyclicaromatic ring system containing about 5 to about 15 ring atoms whereinat least one ring atom is a heteroatom. In some embodiments, theheteroaryl contains 5 to about 10 ring atoms. In some embodiments, theheteroaryl contains 5 or 6 ring atoms. In some embodiments, theheteroaryl is monocyclic. In some embodiments, the heteroatom is N, O,or S. In some embodiments, the heteroaryl contains one heteroatom. Insome embodiments, the heteroaryl contains 1 to 3 N atoms. In someembodiments, the heteroaryl contains one O or S atom and one or two Natoms. In some embodiments, the heteroaryl is furyl, imidazolyl,pyrimidinyl, tetrazolyl, thienyl, pyridyl, pyrrolyl, thiazolyl,isothiazolyl, oxazolyl, isoxazolyl, thiazolyl, quinolinyl, orisoquinolinyl. In some embodiments, the heteroaryl is furyl. In someembodiments, the heteroaryl is substituted.

As used herein, “hydrocarbyl” refers to a monovalent, linear, branched,or cyclic group which contains carbon and hydrogen atoms, and in certainembodiments, is substituted. In some embodiments, the hydrocarbyl isalkyl, alkenyl, alkynyl, aryl, alkaryl, or aralkyl, each optionallysubstituted. In some embodiments, the hydrocarbyl is substituted. Insome embodiments, the hydrocarbyl is not substituted.

As used herein, “inifer” refers to a compound that acts as both aninitiator and a chain transfer agent.

As used herein, “initiator” refers to a compound that provides acarbocation.

As used herein, “ionized polyolefin” refers to a polyolefin containingat least one carbenium ion. In some embodiments, the ionized polyolefinis a tert-halide terminated polyolefin that has been ionized into acationic polyolefin. In some embodiments, the ionized polyolefin is aquasiliving carbocationic polyolefin. In some embodiments, the ionizedpolyolefin is a vinylidene-terminated polyolefin that has been ionizedinto an ionized polyolefin or quasiliving polyolefin. In someembodiments, the ionized polyolefin is a polyolefin containing an olefinthat has been ionized into a quasiliving carbocationic polyolefin or acationic polyolefin. In some embodiments, the ionized polyolefin isderived from an inifer.

As used herein, “Lewis acid” refers to a chemical entity that is capableof accepting a pair of electrons.

As used herein, “metalloid” refers to elements that have properties ofboth metals and non-metals. In some embodiments, the metalloid is boronor silicon.

As used herein, “mole percent” refers to the proportion of the number ofmoles of a particular product of a reaction to the number of moles ofall products of the reaction multiplied by one hundred.

As used herein, “mono-functional initiator” refers to an initiator thatprovides approximately one stoichiometric equivalent of carbocationrelative to initiator. When a mono-functional initiator is used, thechain-end concentration is approximately equal to the initiatorconcentration.

As used herein, “monomer” refers to an olefin that is capable ofcombining with a carbocation to form another carbocation.

As used herein, “multi-functional initiator” refers to an initiator thatprovides approximately x stoichiometric equivalents of carbocationrelative to initiator, wherein x represents the functionality of theinitiator. When a multi-functional initiator is used, when thefunctionality of the initiator equals x, then the chain-endconcentration equals x times the initiator concentration. In someembodiments, x is 2, and the initiator is a bifunctional initiator.

As used herein, “nitroalkane” refers to RNO₂, wherein R is hydrocarbyl.In some embodiments, R is alkyl.

As used herein, “polyolefin” refers to a polymer that comprises at leasttwo olefin monomers. In some embodiments, the polyolefin has a molecularweight from about 300 to in excess of a million g/mol. In someembodiments, the polyolefin has a molecular weight of from about 200 to10,000 g/mol. In some embodiments, the polyolefin has a molecular weightof from about 100,000 to 1,000,000 g/mol. In some embodiments, thepolyolefin has a molecular weight greater than 200 g/mol. In someembodiments, the polyolefin has a molecular weight greater than 400g/mol. In some embodiments, the polyolefin has a molecular weightgreater than 600 g/mol. In some embodiments, the polyolefin has amolecular weight greater than 800 g/mol. In some embodiments, thepolyolefin has a molecular weight greater than 1000 g/mol. In someembodiments, the polyolefin has a molecular weight greater than 5000g/mol. In some embodiments, the polyolefin has a molecular weightgreater than 10,000 g/mol. In some embodiments, the polyolefin has amolecular weight greater than 100,000 g/mol. In some embodiments, thepolyolefin has a molecular weight greater than 500,000 g/mol. In someembodiments, the polyolefin has a molecular weight greater than1,000,000 g/mol.

As used herein, “polyolefin group” refers to monovalent polyolefinsubstituent.

As used herein, “pseudohalide” refers to a substituent that resemblesthe reactivity of a halide substituent, for example, cyano, azido,cyanate, thiocyanate, or isothiocyanate.

As used herein, “quasiliving carbocationic polyolefin” refers to acarbocationic polyolefin that has been formed under quasilivingcarbocationic polymerization conditions.

As used herein, “quasiliving carbocationic polymerization conditions”refers to conditions that allow for quasiliving polymerizations, whichare polymerizations that proceed with minimal irreversible chaintermination and minimal chain transfer. Quasiliving polymerizationsproceed by initiation followed by propagation, wherein propagating(living) species are in equilibrium with non-propagating (non-living)polymer chains.

As used herein, “substituted” refers to the presence of one or moresubstituents. In some embodiments, only one substituent is present. Insome embodiments, the substituent is alkyl. In some embodiments, thesubstituent is alkenyl. In some embodiments, the substituent is alkynyl.In some embodiments, the substituent is aryl. In some embodiments, thesubstituent is alkaryl. In some embodiments, the substituent is aralkyl.In some embodiments, the substituent is halo. In some embodiments, thesubstituent is heteroaryl. In some embodiments, the substituent isheteroalkyl. In some embodiments, the substituent is

In some embodiments, the substituent is

wherein R is alkyl, aryl, aralkyl, or alkaryl. In some embodiments, thesubstituent is furyl. In some embodiments, the substituent is

wherein R¹-R³ are each, independently, optionally substitutedhydrocarbyl. In some embodiments, the substituent is

In some embodiments, the substituent is

wherein R is alkyl, aryl, aralkyl, or alkaryl. In some embodiments, thesubstituent is a pseudohalide.

As used herein, “telechelic polyolefin” refers to a polyolefin having afunctionalized endgroup.

As used herein, “tert-halide terminated polyolefin” refers to apolyolefin that contains at least one tertiary halide end group. In someembodiments, the tert-halide terminated polyolefin has the followingformula:

wherein R is a polyolefin group and X is halo.

As used herein, “thiol” refers to a compound of the following formula:R—SHwherein R is optionally substituted hydrocarbyl.

As used herein, “trinifer” refers to an inifer that is capable ofinitiation and propagation at three separate sites of an inifer. In someembodiments, the initiation and propagation occur simultaneously ornearly simultaneously at the three sites.

As used herein, “vinylidene-terminated polyolefin” refers to apolyolefin that contains at least one vinylidene end group. In someembodiments, the vinylidene-terminated polyolefin has the followingformula:

wherein R¹ is a polyolefin group and R² is optionally substitutedhydrocarbyl or hydrogen. In some embodiments, R² is hydrocarbyl.

4.2 Methods

4.2.1 Overview

In some embodiments, provided here are methods for preparing telechelicpolyolefins.

Without being limited to any theory, in some embodiments, the methodsdescribed herein proceed by the pathway shown in the following scheme:

wherein

R¹ is a polyolefin group;

R² is hydrocarbyl or hydrogen;

R^(A), R^(B), and R^(C) are each, independently, hydrocarbyl orsubstituted hydrocarbyl;

M is a metal, transition metal, or metalloid;

Y is independently halo or alkyl; and

α and β are each, independently, an integer from 1 to 20.

In some embodiments, ⁻M_(α)Y_(β) is derived from a Lewis acid describedherein. In some embodiments, ⁻M_(α)Y_(β) is derived from a titaniumhalide. In some embodiments, ⁻M_(α)Y_(β) is Ti₂Cl₉.

Without being limited to any theory, the following compounds are stableintermediates in the methods disclosed herein at low temperature:

In some embodiments, such intermediates are observable by spectroscopy.

In certain embodiments, provided herein are methods for preparing avinylidene terminated polyolefin, comprising:

-   -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin from step (a) with one or        more disulfides to form an intermediate; and    -   c. reacting the intermediate of step (b) with one or more        alcohols or amines.

In certain embodiments, provided herein are methods for preparing acompound of the formula:

or a mixture thereof;

-   -   wherein R¹ is a polyolefin group;        -   R^(A) and R^(B) are each, independently, alkyl, aryl,            aralkyl, alkaryl,

-   -   -   wherein m is 1-3; n is 1-3; p is 1-3;            -   X is halo or a pseudohalide;            -   R^(x) is alkyl or aryl;            -   R³ is tert-butyl; and            -   R⁴ and R⁵ are each, independently, alkyl, aryl, aralkyl,                or alkaryl; comprising:

    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;

    -   b. reacting the ionized polyolefin from step (a) with one or        more compounds of the formula:        R^(A)—S—S—R^(B)

    -   to form an intermediate; and

    -   c. reacting the intermediate of step (b) with one or more        alcohols, amines, or thiols.

In certain embodiments, provided herein are methods for preparing acompound of the formula:

wherein R¹ is a polyolefin group; and

-   -   R^(C) is alkyl, aryl, aralkyl, alkaryl, substituted alkyl, or        substituted aryl; comprising:    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin with one or more compounds of        the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate;        -   wherein R^(A) and R^(B) are each, independently, alkyl,            aryl, or substituted aryl; and    -   c. reacting the intermediate from step (b) with one or more        compounds of the formula:        R^(C)—SH        4.2.2 Ionized Polyolefins

Ionized polyolefins may be made by any method known to those of skill inthe art. Examples include, but are not limited to, ionizing atert-halide with a Lewis acid; ionizing a preformed polyolefin with aLewis acid in the presence of a proton source; polymerizing an olefinmonomer under quasiliving carbocationic polymerization conditions; orperforming the “inifer” method.

In some embodiments, the ionized polyolefin is a carbocation terminatedpolyolefin. In some embodiments, the ionized polyolefin contains one ormore carbocation end groups. In some embodiments, the ionized polyolefincontains one carbocation end group. In some embodiments, the ionizedpolyolefin contains two carbocation end groups. In some embodiments, theionized polyolefin contains three carbocation end groups. In someembodiments, the ionized polyolefin is a polyisobutylene with a cationicend group. In some embodiments, the ionized polyolefin is a compound ofthe following formula:

(a) Ionized Polyolefins from Tert-Halides

In some embodiments, the ionized polyolefin is derived from atert-halide terminated polyolefin. In some embodiments, the ionizedpolyolefin is derived form a tert-chloride terminated polyolefin,tert-bromide terminated polyolefin, or tert-iodide terminatedpolyolefin. In some embodiments, the ionized polyolefin is derived froma tert-chloride terminated polyolefin or tert-bromide terminatedpolyolefin. In some embodiments, the ionized polyolefin is derived fromtert-chloride terminated polyisobutylene of the following formula:

Tert-halide terminated polyolefins may be made by any method known tothose of skill in the art.

In some embodiments, the ionized polyolefin is generated by contacting atert-halide terminated polyolefin with a Lewis acid. In someembodiments, the ionized polyolefin is generated by contacting atert-chloride terminated polyolefin, tert-bromide terminated polyolefin,or tert-iodide terminated polyolefin with a Lewis acid. In someembodiments, the ionized polyolefin is generated by contacting atert-chloride terminated polyolefin with a Lewis acid.

In some embodiments, the tert-halide is derived from an inifer

(b) Ionized Polyolefins from Preformed Polyolefins

In some embodiments, the ionized polyolefin is derived from a preformedpolyolefin. In some embodiments, such preformed polyolefin contains oneor more double bonds. In some embodiments, such preformed polyolefincontains one double bond. In some embodiments, such preformed polyolefinis a polyisobutylene derivative. In some embodiments, such preformedpolyolefin contains one or more endo olefins.

In some embodiments, the ionized polyolefin is generated by contacting aproton source with a preformed polyolefin in the presence of a Lewisacid. In some embodiments, the ionized polyolefin is generated bycontacting a preformed polyolefin containing one or more double bondswith a proton source in the presence of a Lewis acid. In someembodiments, the ionized polyolefin is generated by contacting apreformed polyolefin containing one double bond with a proton source inthe presence of a Lewis acid. In some embodiments, the ionizedpolyolefin is generated by contacting a polyisobutylene derivative witha proton source in the presence of a Lewis acid. In some embodiments,the ionized polyolefin is generated by contacting a preformed polyolefincontaining one or more endo olefins with a proton source in the presenceof a Lewis acid.

(c) Ionized Polyolefins from the Inifer Method

In some embodiments, the ionized polyolefin is derived from an iniferusing methods known to those of skill in the art. Non-limiting examplesof such methods are described in U.S. Pat. Nos. 4,276,394 and 4,568,732,each of which is incorporated by reference herein. In some embodiments,a monomer is reacted with an inifer carrying at least two tertiaryhalogens under cationic polymerization conditions. In some embodiments,the inifer is a binifer or a trinifer. In some embodiments, the iniferis tricumyl chloride, paradicumyl chloride, or tricumyl bromide.

(d) Ionized Polyolefins from Olefinic Monomers Under Quasi-LivingCarbocationic Polymerization Conditions

In some embodiments, the ionized polyolefin is derived from olefinicmonomers under quasi-living carbocationic conditions. Under suchconditions, a quasi-living carbocationic polyolefin is generated. Suchconditions may be achieved by any quasiliving method known to those ofskill in the art. In some embodiments, a monomer, an initiator, and aLewis acid are used. In some embodiments, an electron donor, common ionsalt, and/or common ion salt precursor is/are used. Non-limitingexamples of such methods are described in EP 206756 B1 and WO2006/110647 A1, both of which are incorporated by reference herein.

In some embodiments, the ionized polyolefin is a quasi-livingcarbocationic polyisobutylene of the following formula:

Some non-limiting examples of reagents and conditions suitable forpolymerizations producing quasi-living polyolefins will be describedbelow.

(i) Initiators

In some embodiments, the initiator is a compound or polyolefin with one,or more than one, end group capable of initiating a cationic olefinpolymerization. For example, the initiator can be a compound of formula(X′—CR_(a)R_(b))_(n)R_(c) wherein R_(a) and R_(b) are independentlyhydrogen, alkyl, aryl, alkaryl, or aralkyl, provided that at least oneof R_(a) or R_(b) is not hydrogen; and R_(c) has a valence of n, and nis an integer of one to 4. X′ is an acetate, etherate, hydroxyl group,or a halogen. In some embodiments, R_(a), R_(b) and R_(c) arehydrocarbon groups containing one carbon atom to about 20 carbon atoms.In some embodiments, R_(a), R_(b) and R_(c) are hydrocarbon groupscontaining one carbon atom to about 8 carbon atoms. In some embodiments,X′ is a halogen. In some embodiments, X′ is chloride. In someembodiments, the structure of R_(a), R_(b) and R_(c) mimics the growingspecies or monomer. In some embodiments, such structure is a 1-halo,1-phenylethane initiator for polystyrene or a 2,4,4-trimethyl pentylhalide initiator for polyisobutylene. In some embodiments, R_(a), R_(b)and R_(c) are each hydrocarbon groups containing one carbon atom toabout 8 carbon atoms for the initiation of an isobutylenepolymerization. In some embodiments, the initiator is a cumyl, dicumylor tricumyl halide.

Some exemplary initiators include 2-chloro-2-phenylpropane, i.e., cumylchloride; 1,3-di-(2-chloro-2-propyl)benzene or1,4-di-(2-chloro-2-propyl)benzene, i.e., collectively dicumylchloride;1,3,5-tri(2-chloro-2-propyl)benzene, i.e., tri(cumylchloride);2,4,4-trimethyl-2-chloropentane; 2-acetoxy-2-phenylpropane, i.e., cumylacetate; 2-propionyl-2-phenyl propane, i.e., cumyl propionate;2-methoxy-2-phenylpropane, i.e., cumylmethyl ether;1,4-di(2-methoxy-2-propyl)benzene, i.e., di(cumylmethyl ether);1,3,5-tri(2-methoxy-2-propyl)benzene, i.e., tri(cumylmethyl ether);2-chloro-2,4,4-trimethyl pentane (TMPC1);1,3-di(2-chloro-2-propyl)benzene; and1,3,-di(2-chloro-2-propyl)-5-tert-butylbenzene (bDCC).

In some embodiments, the initiator can be mono-functional,bi-functional, or multi-functional. Some examples of mono-functionalinitators include 2-chloro-2-phenylpropane, 2-acetoxy-2-phenylpropane,2-propionyl-2-phenylpropane, 2-methoxy-2-phenylpropane,2-ethoxy-2-phenylpropane, 2-chloro-2,4,4-trimethylpentane,2-acetoxy-2,4,4,-trimethylpentane, 2-propionyl-2,4,4-trimethylpentane,2-methoxy-2,4,4-trimethylpentane, 2-ethoxy-2,4,4-trimethylpentane, and2-chloro-2,4,4-trimethylpentane. Some examples of bi-functionalinitiators include 1,3-di(2-chloro-2-propyl)benzene,1,3-di(2-methoxy-2-propyl)benzene, 1,4-di(2-chloro-2-propyl)benzene,1,4-di(2-methoxy-2-propyl)benzene, and5-tert-butyl-1,3,-di(2-chloro-2-propyl)benzene. Some examples ofmulti-functional initiators include 1,3,5-tri(2-chloro-2-propyl)benzeneand 1,3,5-tri(2-methoxy-2-propyl)benzene. In some embodiments, theinitiator is 2-chloro-2,4,4-trimethylpentane,1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene, or dicumyl chloride. Insome embodiments, the initiator is 2-chloro-2,4,4-trimethylpentane.

(ii) Monomers

In some embodiments, the monomer is a hydrocarbon monomer, i.e., acompound containing only hydrogen and carbon atoms, including but notlimited to, olefins and diolefins, and those having from about 2 toabout 20 carbon atoms, e.g., from about 4 to about 8 carbon atoms. Someexemplary monomers include isobutylene, styrene, beta pinene, isoprene,butadiene, 2-methyl-1-butene, 3-methyl-1-butene, and 4-methyl-1-pentene.In some embodiments, the monomer is isobutylene or styrene. In someembodiments, the monomer is isobutylene. In some embodiments, themonomer is styrene.

In some embodiments, a mixture of monomers is used. In some embodiments,a mixture of 2 or more monomers is used. In some embodiments, a mixtureof 2 monomers is used. In some embodiments, a mixture of 3 monomers isused. In some embodiments, a mixture of 4 monomers is used.

In some embodiments, the monomers are polymerized to produce polymers ofdifferent, but substantially uniform molecular weights. In someembodiments, the molecular weight of the polymer is from about 300 to inexcess of a million g/mol. In some embodiments, such polymers are lowmolecular weight liquid or viscous polymers having a molecular weight offrom about 200 to 10,000 g/mol, or solid waxy to plastic, or elastomericmaterials having molecular weights of from about 100,000 to 1,000,000g/mol, or more.

(iii) Lewis Acids

In the methods provided herein, in some embodiments, the Lewis acid is anon-protic acid, e.g., a metal halide or non-metal halide.

Some examples of metal halide Lewis acids include a titanium (IV)halide, a zinc (II) halide, a tin (IV) halide, and an aluminum (III)halide, e.g., titanium tetrabromide, titanium tetrachloride, zincchloride, AlBr₃, and alkyl aluminum halides such as ethyl aluminumdichloride and methyl aluminum bromide. Some examples of non-metalhalide Lewis Acids include an antimony (VI) halide, a gallium (III)halide, or a boron (III) halide, e.g., boron trichloride, or a trialkylaluminum compound such as trimethyl aluminum.

Mixtures of two, or more than two, Lewis acids can also used. In oneexample, a mixture of an aluminum (III) halide and a trialkyl aluminumcompound is used. In some embodiments, the stoichiometric ratio ofaluminum (III) halide to trialkyl aluminum is greater than 1, while inother embodiments, the stoichiometric ratio of aluminum (III) halide totrialkyl aluminum is less than 1. For example, a stoichiometric ratio ofabout 1:1 aluminum (III) halide to trialkyl aluminum compound; astoichiometric ratio of 2:1 aluminum (III) halide to trialkyl aluminumcompound; or a stoichiometric ratio of 1:2 aluminum (III) halide totrialkyl aluminum can be used. In another example, a mixture of aluminumtribromide and trimethyl aluminum is used.

In some embodiments, the Lewis acid can be added in a suitable number ofaliquots, e.g., in one aliquot or more than one aliquot, e.g., twoaliquots.

(iv) Electron Donors

As is understood to one of ordinary skill in the art, some electrondonors are capable of converting traditional polymerization systems intoquasiliving polymerization systems. In some embodiments, the methodsdescribed herein are performed in the presence of an electron donor.

In some embodiments, the electron donor is capable of complexing withLewis acids. In some embodiments, the electron donor is a base and/ornucleophile. In some embodiments, the electron donor is capable ofabstracting or removing a proton. In some embodiments, the electrondonor is an organic base. In some embodiments, the electron donor is anamide. In some embodiments, the electron donor is N,N-dimethylformamide,N,N-dimethylacetamide, or N,N-diethylacetamide. In some embodiments, theelectron donor is a sulfoxide. In some embodiments, the electron donoris dimethyl sulfoxide. In some embodiments, the electron donor is anester. In some embodiments, the electron donor is methyl acetate orethyl acetate. In some embodiments, the electron donor is a phosphatecompound. In some embodiments, the electron donor is trimethylphosphate, tributyl phosphate, or triamide hexamethylphosphate. In someembodiments, the electron donor is an oxygen-containing metal compound.In some embodiments, the electron donor is tetraisopropyl titanate.

In some embodiments, the electron donor is pyridine or a pyridinederivative. In some embodiments, the electron donor is a compound offormula:

wherein R₁, R₂, R₃, R₄, and R₅ are each, independently, hydrogen orhydrocarbyl; or R₁ and R₂, or R₂ and R₃, or R₃ and R₄, or R₄ and R₅independently form a fused aliphatic ring of about 3 to about 7 carbonatoms or a fused aromatic ring of about 5 to about 7 carbon atoms. Insome embodiments, R₁ and R₅ are each, independently, hydrocarbyl, andR₂-R₄ are hydrogen.

In some embodiments, the electron donor is 2,6-di-tert-butylpyridine,2,6-lutidine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine,2-methylpyridine, or pyridine.

(v) Common Ion Salts and Ion Salt Precursors

In some embodiments, common ion salts or salt precursors may beoptionally added to the reaction mixture in addition to or inreplacement of the electron donor. In some embodiments, such salts maybe used to increase the ionic strength, suppress free ions, and interactwith ligand exchange. In some embodiments, the common ion salt precursoris tetra-n-butylammonium chloride. In some embodiments, the common ionsalt precursor is tetra-n-butylammonium iodide In some embodiments, theconcentration of the common ion salts or salt precursors in the totalreaction mixture may be in the range from about 0.0005 moles per literto about 0.05 moles per liter. In some embodiments, the concentration ofthe common ion salts or salt precursors is in the range from about0.0005 moles per liter to about 0.025 moles per liter. In someembodiments, the concentration of the common ion salt or salt precursorsis in the range from about 0.001 moles per liter to about 0.007 molesper liter.

4.2.3 Preparation of Vinylidene-Terminated Polyolefins

In some embodiments, provided herein are methods for preparing avinylidene terminated polyolefin comprising:

-   -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin from step (a) with one or        more disulfides to form an intermediate; and    -   c. reacting the intermediate of step (b) with one or more        alcohols or amines.

In some embodiments, the vinylidene terminated polyolefin is avinylidene terminated polyisobutylene.

(a) Disulfides

In some embodiments, more than one disulfide is used. In someembodiments, one disulfide is used.

In some embodiments, the disulfide is a compound of the formula:R^(A)—S—S—R^(B)wherein R^(A) and R^(B) are each, independently, alkyl, aryl, aralkyl,alkaryl,

-   -   wherein m is 1-3; n is 1-3; p is 1-3;        -   X is halo or a pseudohalide;        -   R^(x) is alkyl, aryl, aralkyl, or alkaryl;        -   R³ is tert-butyl; and        -   R⁴ and R⁵ are each, independently, alkyl, aryl, aralkyl, or            alkaryl.

In some embodiments, the disulfide is a compound of the formula:R^(A)—S—S—R^(B):wherein R^(A) and R^(B) are each, independently, alkyl, aryl, alkaryl,

wherein n is 1-3; p is 1-3;

-   -   X is halo;    -   R³ is tert-butyl;    -   R⁴ and R⁵ are each, independently, aryl or alkyl; and    -   R^(x) is alkyl or aryl.

In some embodiments, R^(A) and R^(B) are identical.

In some embodiments, R^(A) and R^(B) are alkyl, aryl or alkaryl.

In some embodiments, R^(A) and R^(B) are alkyl.

In some embodiments, R^(A) and R^(B) are alkyl of 1 to about 10 carbons.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, propyl,tert-butyl, isopropyl, phenyl, or tolyl.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, tert-butyl,isopropyl, or tolyl.

In some embodiments, R^(A) and R^(B) are ethyl, tert-butyl, isopropyl,or tolyl.

In some embodiments, R^(A) and R^(B) are isopropyl or tert-butyl.

In some embodiments, R^(A) and R^(B) are isopropyl.

In some embodiments, R^(A) and R^(B) are tert-butyl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1-2. In further embodiments, n is 1. Infurther embodiments, R^(x) is alkyl. In further embodiments, R^(x) isaryl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1. In further embodiments, n is 2. Infurther embodiments, n is 3.

In further embodiments, X is F, Cl, or Br. In further embodiments, X isCl or Br. In further embodiments, X is Cl. In further embodiments, X isBr.

In some embodiments, R^(A) and R^(B) are

In further embodiments, p is 1. In further embodiments, p is 2. Infurther embodiments, p is 3.

In further embodiments, R⁴ and R⁵ are identical.

In further embodiments, R⁴ and R⁵ are aryl. In further embodiments, R⁴and R⁵ are alkyl. In certain embodiments, R⁴ and R⁵ are tertiary alkyl.

In some embodiments, R⁴ and R⁵ are phenyl or methyl. In someembodiments, R⁴ and R⁵ are phenyl.

(b) Alcohols

In some embodiments, the intermediate of step (b) is reacted with one ormore alcohols. In some embodiments, more than one alcohol is used. Insome embodiments, one alcohol is used.

In some embodiments, the alcohol is a compound of the formula:R—OHwherein R is alkyl of 1-8 carbons.In some embodiments, the alkyl is a straight hydrocarbon chain.

In some embodiments, the alcohol is methanol, ethanol, isopropanol,2-ethylhexanol, or sec-butanol.

In some embodiments, the alcohol is ethanol, isopropanol,2-ethylhexanol, or sec-butanol.

In some embodiments, the alcohol is methanol or isopropanol

In some embodiments, the alcohol is methanol.

(c) Amines

In some embodiments, the intermediate of step (b) is reacted with one ormore amines. In some embodiments, more than one amine is used. In someembodiments, one amine is used.

In some embodiments, the amine is n-butylamine, 2-ethylhexylamine,tert-amylamine, triethylamine, or dibutylamine.

(d) Product Distribution

In some embodiments, the methods described herein selectively providevinylidene-terminated polyolefins. In some embodiments,vinylidene-terminated polyolefins, polyolefins containing endo olefins,tert-halide polyolefins, coupled polyolefins, and sulfide-terminatedpolyolefins are reaction products. In some embodiments, vinylideneterminated polyolefins are the major products, and polyolefinscontaining endo olefins, tert-halide polyolefins, coupled polyolefins,and sulfide-terminated polyolefins are the minor products.

In some embodiments, the vinylidene terminated polyolefin formed is atleast 10 mole percent of all products. In some embodiments, thevinylidene terminated polyolefin formed is at least 20 mole percent ofall products. In some embodiments, the vinylidene terminated polyolefinformed is at least 40 mole percent of all products. In some embodiments,the vinylidene terminated polyolefin formed is at least 60 mole percentof all products. In some embodiments, the vinylidene terminatedpolyolefin formed is at least 70 mole percent of all products. In someembodiments, the vinylidene terminated polyolefin formed is at least 80mole percent of all products. In some embodiments, the vinylideneterminated polyolefin formed is at least 85 mole percent of allproducts.

In some embodiments, the vinylidene terminated polyolefin formed is atmost 10 mole percent of all products. In some embodiments, thevinylidene terminated polyolefin formed is at most 20 mole percent ofall products. In some embodiments, the vinylidene terminated polyolefinformed is at most 40 mole percent of all products. In some embodiments,the vinylidene terminated polyolefin formed is at most 60 mole percentof all products. In some embodiments, the vinylidene terminatedpolyolefin formed is at most 70 mole percent of all products. In someembodiments, the vinylidene terminated polyolefin formed is at most 80mole percent of all products. In some embodiments, the vinylideneterminated polyolefin formed is at most 85 mole percent of all products.

4.2.4 Preparation of Sulfide-Terminated Polyolefins

(a) Preparation of Sulfide-Terminated Polyolefins Via TerminationReaction with Alcohols or Amines.

In some embodiments, provided herein are methods for preparing asulfide-terminated polyolefin of the formula:

or a mixture thereof;

-   -   wherein R¹ is a polyolefin group;        -   R^(A) and R^(B) are each, independently, alkyl, aryl,            aralkyl, alkaryl,

-   -   -   wherein m is 1-3; n is 1-3; p is 1-3;            -   X is halo or a pseudohalide;            -   R^(x) is alkyl or aryl;            -   R³ is tert-butyl; and            -   R⁴ and R⁵ are each, independently, alkyl, aryl, aralkyl,                or alkaryl, comprising

    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;

    -   b. reacting the ionized polyolefin from step (a) with one or        more compounds of the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate; and

    -   c. reacting the intermediate of step (b) with one or more        alcohols or amines.

In some embodiments, provided herein are methods for preparing asulfide-terminated polyolefin of the formula:

or a mixture thereof;

-   -   wherein R¹ is a polyolefin group;        -   R^(A) and R^(B) are each, independently, alkyl, aryl,            alkaryl,

-   -   -   wherein n is 1-3; p is 1-3;            -   X is halo or a pseudohalide;            -   R³ is tert-butyl;            -   R⁴ and R⁵ are each, independently, aryl or alkyl; and            -   R^(x) is alkyl or aryl, comprising:

    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;

    -   b. reacting the ionized polyolefin from step (a) with one or        more compounds of the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate; and

    -   c. reacting the intermediate of step (b) with one or more        alcohols or amines.

In some embodiments, R¹ is a polyisobutylene group.

(i) Disulfides

In some embodiments, more than one compound of the formulaR^(A)—S—S—R^(B) is used. In some embodiments, one compound of theformula R^(A)—S—S—R^(B) is used.

In some embodiments, R^(A) and R^(B) are identical.

In some embodiments, R^(A) and R^(B) are alkyl or alkaryl. In someembodiments, R^(A) and R^(B) are alkyl. In some embodiments, R^(A) anR^(B) are alkyl of 1 to about 10 carbons.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, propyl,isopropyl, phenyl, or tolyl.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, isopropyl, ortolyl.

In some embodiments, R^(A) and R^(B) are isopropyl or tolyl.

In some embodiments, R^(A) and R^(B) are isopropyl.

In some embodiments, R^(A) and R^(B) are tolyl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1-2. In further embodiments, n is 1.

In some embodiments, R^(x) is alkyl. In some embodiments, R^(x) is aryl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1. In further embodiments, n is 2. Infurther embodiments, n is 3.

In further embodiments, X is F, Cl, or Br. In further embodiments, X isCl or Br. In further embodiments, X is Cl. In further embodiments, X isBr.

In some embodiments, R^(A) and R^(B) are

In further embodiments, p is 1. In further embodiments, p is 2. Infurther embodiments, p is 3.

In further embodiments, R⁴ and R⁵ are identical.

In further embodiments, R⁴ and R⁵ are aryl. In further embodiments, R⁴and R⁵ are alkyl. In certain embodiments, R⁴ and R⁵ are tertiary alkyl.

In some embodiments, R⁴ and R⁵ are phenyl or methyl. In someembodiments, R⁴ and R⁵ are phenyl.

(ii) Alcohols

In some embodiments, the intermediate of step (b) is reacted with one ormore alcohols. In some embodiments, one alcohol is used. In someembodiments, more than one alcohol is used.

In some embodiments, the alcohol isR—OHwherein R is alkyl of 1-8 carbons.

In some embodiments, the alcohol is methanol or isopropanol. In someembodiments, the alcohol is methanol.

(iii) Amines

In some embodiments, the intermediate of step (b) is reacted with one ormore amines. In some embodiments, one amine is used. In someembodiments, more than one amine is used.

In some embodiments, the amine is

wherein R⁶ is alkyl; and R⁷ and R⁸ are each, independently, hydrogen oralkyl of 1-8 carbons.

In some embodiments, R⁶ is alkyl of 1-8 carbons. In some embodiments, R⁶is butyl,

or ethyl.

In some embodiments, R⁶ is butyl.

In some embodiments, R⁷ and R⁸ are hydrogen. In some embodiments, R⁷ ishydrogen.

In some embodiments, R⁷ and R⁸ are each, independently, alkyl of 1-8carbons.

In some embodiments, R⁶, R⁷, and R⁸ are identical. In some embodiments,R⁷ and R⁸ are identical.

In some embodiments, R⁷ is methyl, ethyl, or butyl. In some embodiments,R⁷ is methyl. In some embodiments, R⁷ is ethyl. In some embodiments, R⁷is butyl.

In some embodiments, R⁸ is methyl, ethyl, or butyl. In some embodiments,R⁸ is methyl. In some embodiments, R⁸ is ethyl. In some embodiments, R⁸is butyl.

In some embodiments, the amine is n-butylamine, 2-ethylhexylamine,tert-amylamine, triethylamine, or dibutylamine. In some embodiments, theamine is triethylamine.

(iv) Product Distribution

In some embodiments, the methods described herein selectively providesulfide-terminated polyolefins of the formula:

or a mixture thereof.

In some embodiments, vinylidene-terminated polyolefins, polyolefinscontaining endo olefins, tert-halide polyolefins, coupled polyolefins,and sulfide-terminated polyolefins are reaction products. In someembodiments, sulfide-terminated polyolefins are the major products, andpolyolefins containing endo olefins, tert-halide polyolefins, coupledpolyolefins, and vinylidene-terminated polyolefins are the minorproducts.

In further embodiments, the sulfide terminated polyolefins formed are atleast 10 mole percent of all products. In some embodiments, the sulfideterminated polyolefins formed are at least 20 mole percent of allproducts. In some embodiments, the sulfide terminated polyolefins formedare at least 40 mole percent of all products. In some embodiments, thesulfide terminated polyolefins formed are at least 60 mole percent ofall products. In some embodiments, the sulfide terminated polyolefinsformed are at least 70 mole percent of all products. In someembodiments, the sulfide terminated polyolefins formed are at least 80mole percent of all products. In some embodiments, the sulfideterminated polyolefins formed are at least 85 mole percent of allproducts. In some embodiments, the sulfide terminated polyolefins formedare at least 90 mole percent of all products. In some embodiments, thesulfide terminated polyolefins formed are at least 95 mole percent ofall products.

In further embodiments, the sulfide terminated polyolefins formed are atmost 10 mole percent of all products. In some embodiments, the sulfideterminated polyolefins formed are at most 20 mole percent of allproducts. In some embodiments, the sulfide terminated polyolefins formedare at most 40 mole percent of all products. In some embodiments, thesulfide terminated polyolefins formed are at most 60 mole percent of allproducts. In some embodiments, the sulfide terminated polyolefins formedare at most 70 mole percent of all products. In some embodiments, thesulfide terminated polyolefins formed are at most 80 mole percent of allproducts. In some embodiments, the sulfide terminated polyolefins formedare at most 85 mole percent of all products. In some embodiments, thesulfide terminated polyolefins formed are at most 90 mole percent of allproducts. In some embodiments, the sulfide terminated polyolefins formedare at most 95 mole percent of all products.

(b) Preparation of Sulfide-Terminated Polyolefins Via TerminationReaction with Thiols

(i) Sulfide-Terminated Polyolefins Via Disulfide Addition

In some embodiments, provided herein are methods for preparing asulfide-terminated polyolefin of the formula:

or a mixture thereof;

-   -   wherein R¹ is a polyolefin group;        -   R^(A) and R^(B) are each, independently, alkyl, aryl,            aralkyl, alkaryl,

-   -   -   wherein m is 1-3; n is 1-3; p is 1-3;            -   X is halo or a pseudohalide;            -   R^(x) is alkyl or aryl;            -   R³ is tert-butyl; and            -   R⁴ and R⁵ are each, independently, alkyl, aryl, aralkyl,                or alkaryl, comprising

    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;

    -   b. reacting the ionized polyolefin from step (a) with one or        more compounds of the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate; and

    -   c. reacting the intermediate of step (b) with one or more        thiols.

In some embodiments, provided herein are methods for preparing asulfide-terminated polyolefin of the formula:

or a mixture thereof;

-   -   wherein R¹ is a polyolefin group;        -   R^(A) and R^(B) are each, independently, alkyl, aryl,            alkaryl,

-   -   -   wherein m is 1-3; n is 1-3; p is 1-3;            -   X is halo;            -   R³ is tert-butyl; and            -   R⁴ and R⁵ are each, independently, aryl or alkyl;

comprising:

-   -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin from step (a) with one or        more compounds of the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate; and    -   c. reacting the intermediate of step (b) with one or more        thiols.

In some embodiments, R¹ is a polyisobutylene group.

1. Disulfides

In some embodiments, one compound of the formula R^(A)—S—S—R^(B) isused. In some embodiments, more than one compound of the formulaR^(A)—S—S—R^(B) is used.

In some embodiments, R^(A) and R^(B) are identical.

In some embodiments, R^(A) and R^(B) are alkyl or alkaryl. In someembodiments, R^(A) and R^(B) are alkyl. In some embodiments, R^(A) andR^(B) are alkyl of 1 to about 10 carbons.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, propyl,isopropyl, phenyl, or tolyl.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, isopropyl, ortolyl.

In some embodiments, R^(A) and R^(B) are isopropyl or tolyl.

In some embodiments, R^(A) and R^(B) are isopropyl.

In some embodiments, R^(A) and R^(B) are tolyl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1-2. In further embodiments, n is 1

In some embodiments, R^(x) is alkyl. In some embodiments, R^(x) is aryl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1. In further embodiments, n is 2. Infurther embodiments, n is 3.

In further embodiments, X is F, Cl, or Br. In further embodiments, X isCl or Br. In further embodiments, X is Cl. In further embodiments, X isBr.

In some embodiments, R^(A) and R^(B) are

In further embodiments, p is 1. In further embodiments, p is 2. Infurther embodiments, p is 3.

In further embodiments, R⁴ and R⁵ are identical.

In further embodiments, R⁴ and R⁵ are aryl. In further embodiments, R⁴and R⁵ are alkyl. In certain embodiments, R⁴ and R⁵ are tertiary alkyl.

In some embodiments, R⁴ and R⁵ are phenyl or methyl. In someembodiments, R⁴ and R⁵ are phenyl.

2. Thiols

In some embodiments, one thiol is used. In some embodiments, more thanone thiol is used.

In some embodiments, the thiol has the formula R^(C1)—SH; wherein R^(C1)is alkyl, aryl, aralkyl, alkaryl, substituted alkyl, or substitutedaryl.

In some embodiments, the R^(C1) is alkyl of 1-6 carbon atoms. In someembodiments, the R^(C1) is alkyl of 1-3 carbon atoms.

In some embodiments, the thiol is ethanethiol or n-propanethiol.

In some embodiments, the disulfide is diisopropyldisulfide and the thiolis ethanethiol. In some embodiments, the disulfide is ditolyldisulfideand the thiol is n-propanethiol.

3. Product Distribution

In some embodiments, the methods described herein selectively providesulfide-terminated polyolefins of the formula:

or a mixture thereof.

In some embodiments, vinylidene-terminated polyolefins, polyolefinscontaining endo olefins, tert-halide polyolefins, coupled polyolefins,sulfide-terminated polyolefins derived from disulfide addition, andsulfide-terminated polyolefins derived from thiol addition are reactionproducts. In some embodiments, sulfide-terminated polyolefins, whereinthe sulfide moiety is derived from the disulfide reagent, are the majorproducts. Polyolefins containing endo olefins, tert-halide polyolefins,coupled polyolefins, vinylidene-terminated polyolefins, andsulfide-terminated polyolefins, wherein the sulfide moiety is derivedfrom the thiol addition, are the minor products.

In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at least 10 mole percent of all products.In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at least 20 mole percent of all products.In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at least 40 mole percent of all products.In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at least 60 mole percent of all products.In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at least 70 mole percent of all products.In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at least 80 mole percent of all products.In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at least 85 mole percent of all products.

In some embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at most 10 mole percent of all products. Insome embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at most 20 mole percent of all products. Insome embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at most 40 mole percent of all products. Insome embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at most 60 mole percent of all products. Insome embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at most 70 mole percent of all products. Insome embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at most 80 mole percent of all products. Insome embodiments, the sulfide terminated polyolefins derived fromdisulfide addition formed is at most 85 mole percent of all products.

(ii) Sulfide-Terminated Polyolefins Via Thiol Addition

In certain embodiments, provided herein are methods for preparing asulfide-terminated polyolefin of the formula:

wherein R¹ is a polyolefin group; and

-   -   R^(C2) is alkyl, aryl, aralkyl, alkaryl, substituted alkyl, or        substituted aryl;        comprising:    -   a. ionizing a polyolefin in the presence of a Lewis acid or        mixture of Lewis acids to form an ionized polyolefin;    -   b. reacting the ionized polyolefin with one or more compounds of        the formula:        R^(A)—S—S—R^(B)        -   to form an intermediate;        -   wherein R^(A) and R^(B) are each, independently, alkyl,            aryl, aralkyl, or alkaryl; and    -   c. reacting the intermediate from step (b) with one or more        compounds of the formula R^(C2)—SH.

In some embodiments, R¹ is a polyisobutylene group.

1. Disulfides

In some embodiments, one compound of the formula R^(A)—S—S—R^(B) isused. In some embodiments, more than one compound of the formulaR^(A)—S—S—R^(B) is used.

In some embodiments, R^(A) and R^(B) are each, independently, alkyl,aryl, aralkyl,

alkaryl,

wherein m is 1-3; n is 1-3; p is 1-3;

-   -   X is halo or a pseudohalide;    -   R^(x) is alkyl or aryl;    -   R³ is tert-butyl; and    -   R⁴ and R⁵ are each, independently, alkyl, aryl, aralkyl, or        alkaryl.

In some embodiments, R^(A) and R^(B) are each, independently, alkyl,aryl, alkaryl,

wherein n is 1-3; p is 1-3;

-   -   X is halo;    -   R³ is tert-butyl;    -   R⁴ and R⁵ are each, independently, aryl or alkyl; and    -   R^(x) is alkyl or aryl.

In some embodiments, R^(A) and R^(B) are identical.

In some embodiments, R^(A) and R^(B) are alkyl or alkaryl. In someembodiments, R^(A) and R^(B) are alkyl.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, propyl,tert-butyl, isopropyl, phenyl, or tolyl.

In some embodiments, R^(A) and R^(B) are methyl, ethyl, tert-butyl,isopropyl, or tolyl.

In some embodiments, R^(A) and R^(B) are isopropyl or tolyl.

In some embodiments, R^(A) and R^(B) are isopropyl.

In some embodiments, R^(A) and R^(B) are tolyl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1-2. In further embodiments, n is 1. Infurther embodiments, R^(x) is alkyl. In further embodiments, R^(x) isaryl.

In some embodiments, R^(A) and R^(B) are

In further embodiments, n is 1. In further embodiments, n is 2. Infurther embodiments, n is 3.

In further embodiments, X is F, Cl, or Br. In further embodiments, X isCl or Br. In further embodiments, X is Cl. In further embodiments, X isBr.

In some embodiments, R^(A) and R^(B) are

In further embodiments, p is 1. In further embodiments, p is 2. Infurther embodiments, p is 3.

In further embodiments, R⁴ and R⁵ are identical.

In further embodiments, R⁴ and R⁵ are aryl. In further embodiments, R⁴and R⁵ are alkyl. In certain embodiments, R⁴ and R⁵ are tertiary alkyl.

In some embodiments, R⁴ and R⁵ are phenyl or methyl. In someembodiments, R⁴ and R⁵ are phenyl.

2. Thiols

In some embodiments, one thiol is used. In some embodiments, more thanone thiol is used.

In some embodiments, the thiol has the formula R^(C2)—SH; wherein R^(C2)is alkyl, aryl, aralkyl, alkaryl, substituted alkyl, or substitutedaryl.

In some embodiments, R^(C2) is alkyl of 1-6 carbons.

In some embodiments, R^(C2) is alkyl of 1-3 carbons.

In some embodiments, the thiol is ethanethiol or n-propanethiol.

In some embodiments, the thiol is n-propanethiol.

In some embodiments, the disulfide is diisopropyldisulfide and the thiolis n-propanethiol. In some embodiments, the disulfide isdiisopropyldisulfide and the thiol ethanethiol.

3. Product Distribution

In some embodiments, the methods described herein selectively providesulfide-terminated polyolefins of the formula:

In some embodiments, vinylidene-terminated polyolefins, polyolefinscontaining endo olefins, tert-halide polyolefins, coupled polyolefins,sulfide-terminated polyolefins derived from disulfide addition, andsulfide-terminated polyolefins derived from thiol addition are reactionproducts. In some embodiments, sulfide-terminated polyolefins, whereinthe sulfide moiety is derived from thiol addition, are the majorproducts. Polyolefins containing endo olefins, tert-halide polyolefins,coupled polyolefins, vinylidene-terminated polyolefins, andsulfide-terminated polyolefins, wherein the sulfide moiety is derivedfrom the disulfide reagent, are the minor products.

In some embodiments, the sulfide terminated polyolefin derived fromthiol addition formed is at least 10 mole percent of all products. Insome embodiments, the sulfide terminated polyolefin derived from thioladdition formed is at least 20 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at least 40 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at least 60 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at least 70 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at least 80 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at least 85 mole percent of all products.

In some embodiments, the sulfide terminated polyolefin derived fromthiol addition formed is at most 10 mole percent of all products. Insome embodiments, the sulfide terminated polyolefin derived from thioladdition formed is at most 20 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at most 40 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at most 60 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at most 70 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at most 80 mole percent of all products. In someembodiments, the sulfide terminated polyolefin derived from thioladdition formed is at most 85 mole percent of all products.

4.2.5 Diluents

In some embodiments of the methods described herein, the methods areperformed in a diluent. In some embodiments, the diluent is a singlecompound or a mixture of two or more compounds. In some embodiments, thediluent completely dissolves the reaction components or partiallydissolves the reaction components. In some embodiments, the diluentcompletely or nearly completely dissolves the reaction components. Insome embodiments, the diluent completely dissolves the reactioncomponents. In some embodiments, the diluent nearly completely dissolvesthe reaction components.

In some embodiments, the diluent has a low boiling point and/or lowfreezing point. In some embodiments, the diluent is a normal alkane. Insome embodiments, the diluent is propane, normal butane, normal pentane,normal hexane, normal heptane, normal octane, normal nonane or normaldecane. In some embodiments, the diluent is normal hexane or normalpentane. In some embodiments, the diluent is normal hexane. In someembodiments, the diluent is a branched alkane. In some embodiments, thealkane is isobutane, isopentane, neopentane, isohexane, 3-methylpentane,2,2-dimethylbutane, or 2,3-dimethylbutane. In some embodiments, thealkane is a nitroalkane.

In some embodiments, the diluent is an alkyl halide. In someembodiments, the diluent is an alkyl monohalide or an alkyl polyhalide.In some embodiments, the diluent is chloroform, ethylchloride, n-butylchloride, methylene chloride, methyl chloride, 1,2-dichloroethane,1,1,2,2-tetrachloroethane, carbon tetrachloride, 1,1-dichloroethane,n-propyl chloride, iso-propyl chloride, 1,2-dichloropropane, or1,3-dichloropropane. In some embodiments, the diluent is methylenechloride or methyl chloride. In some embodiments, the diluent is methylchloride. In some embodiments, the diluent is an alkene or halogenatedalkene. In some embodiments, the diluent is vinyl chloride,1,1-dichloroethene, or 1,2-dichloroethene.

In some embodiments, the diluent is a substituted benzene. In someembodiments, the diluent is benzene. In some embodiments, the diluent istoluene.

In some embodiments, the diluent is carbon disulfide, sulfur dioxide,acetic anhydride, acetonitrile, benzene, toluene, ethylbenzene,methylcyclohexane, chlorobenzene, or a nitroalkane.

In some embodiments, the diluent is a mixture of two or more compounds.In some embodiments, the diluent is a mixture of hexane and methylchloride. In further embodiments, such mixture is from about 1:9 toabout 9:1 hexane:methyl chloride by volume. In further embodiments, suchmixture is from about 1:2 to about 2:1 hexane:methyl chloride by volume.In further embodiments, such mixture is from about 1:1.6 to about 1.6:1hexane:methyl chloride by volume. In further embodiments, such mixtureis from about 1:1.4 to about 1.4:1 hexane:methyl chloride by volume. Infurther embodiments, such mixture is about 1:1 hexane:methyl chloride byvolume.

4.2.6 Temperature

In some embodiments, the methods described herein are performed at atemperature from about −120° C. to about 0° C. In some embodiments, themethods described herein are performed at a temperature from about −110°C. to about −10° C. In some embodiments, the methods described hereinare performed at a temperature from about −100° C. to about −20° C. Insome embodiments, the methods described herein are performed at atemperature from about −90° C. to about −30° C. In some embodiments, themethods described herein are performed at a temperature from about −80°C. to about −40° C. In some embodiments, the methods described hereinare performed at a temperature from about −70° C. to about −40° C. Insome embodiments, the methods described herein are performed at atemperature from about −60° C. to about −40° C. In some embodiments, themethods described herein are performed at a temperature of −40° C., −45°C., −60° C., or −80° C. In some embodiments, the methods describedherein are performed at a temperature of −40° C. In some embodiments,the methods described herein are performed at a temperature of −45° C.In some embodiments, the methods described herein are performed at atemperature of −60° C. In some embodiments, the methods described hereinare performed at a temperature of −80° C.

4.2.7 Concentrations

The chain end concentration of the methods described herein are notlimited by the disclosed examples. In some embodiments, the chain endconcentration is less than 0.010 M. In some embodiments, the chain endconcentration is less than 0.050 M. In some embodiments, the chain endconcentration is less than 0.10 M. In some embodiments, the chain endconcentration is less than 0.5 M. In some embodiments, the chain endconcentration is less than 1.0 M. In some embodiments, the chain endconcentration is greater than 0.001 M.

In some embodiments, the molar concentration of disulfide is from about1 to about 10 times the molar concentration of chain ends. In someembodiments, the molar concentration of disulfide is from about 1.1 toabout 8 times the molar concentration of chain ends. In someembodiments, the molar concentration of disulfide is from about 1.1 toabout 5 times the molar concentration of chain ends. In someembodiments, the molar concentration of disulfide is from about 1.1 toabout 4 times the molar concentration of chain ends. In someembodiments, the molar concentration of disulfide is from about 1.1 toabout 3 times the molar concentration of chain ends. In someembodiments, the molar concentration of disulfide is from about 1.1 toabout 2 times the molar concentration of chain ends.

In some embodiments, the molar concentration of Lewis acid is from about0.5 to about 20 times the molar concentration of chain ends. In someembodiments, the molar concentration of Lewis acid is from about 0.5 toabout 15 times the molar concentration of chain ends. In someembodiments, the molar concentration of Lewis acid is from about 1.0 toabout 10 times the molar concentration of chain ends. In someembodiments, the molar concentration of Lewis acid is from about 1.0 toabout 8 times the molar concentration of chain ends. In someembodiments, the molar concentration of Lewis acid is from about 2 toabout 5 times the molar concentration of chain ends.

In some embodiments, the electron donor concentration is less than halfthe concentration of Lewis acid. In some embodiments, the electron donorconcentration is less than 0.4 times the Lewis acid concentration. Insome embodiments, the electron donor concentration is less than 0.3times the Lewis acid concentration. In some embodiments, the electrondonor concentration is less than 0.2 times the Lewis acid concentration.In some embodiments, the electron donor concentration is less than 0.1times the Lewis acid concentration.

4.3 Compounds

Provided herein are compounds of the formula:

wherein R¹ is a polyolefin group; and

-   -   R^(D) is alkyl of 1 to 7 carbons, substituted alkyl,        unsubstituted aryl, alkaryl, aralkyl,

-   -   -   wherein m is 1-3; n is 1-3; p is 1-3;            -   X is halo or a pseudohalide;            -   R³ is tert-butyl;            -   R⁴ and R⁵ are each, independently, aryl or alkyl; and            -   R^(x) is hydrocarbyl.

In some embodiments, R^(D) is alkyl of 1 to 7 carbons or substitutedalkyl. In some embodiments, R^(D) is alkyl of 1 to 7 carbons. In someembodiments, R^(D) is alkyl of 1 carbon. In some embodiments, R^(D) isalkyl of 2 carbons. In some embodiments, R^(D) is alkyl of 3 carbons. Insome embodiments, R^(D) is alkyl of 4 carbons. In some embodiments,R^(D) is alkyl of 5 carbons. In some embodiments, R^(D) is alkyl of 6carbons. In some embodiments, R^(D) is alkyl of 7 carbons. In someembodiments, R^(D) is substituted alkyl. In some embodiments, R^(D) issubstituted alkyl of 1 to 7 carbons.

In some embodiments, R^(D) is substituted alkyl of at least 3 carbons.In some embodiments, R^(D) is substituted alkyl of 3-7 carbons. In someembodiments, R^(D) is substituted alkyl of 3 carbons. In someembodiments, R^(D) is substituted alkyl of 4 carbons. In someembodiments, R^(D) is substituted alkyl of 5 carbons. In someembodiments, R^(D) is substituted alkyl of 6 carbons. In someembodiments, R^(D) is substituted alkyl of 7 carbons.

In some embodiments, R^(D) is alkaryl. In some embodiments, R^(D) isalkaryl of at least 8 carbons. In some embodiments, R^(D) is alkaryl of8 to about 12 carbons. In some embodiments, R^(D) is alkaryl of at least14 carbons.

In some embodiments, R^(D) is methyl, ethyl, tert-butyl, isopropyl, ortolyl. In some embodiments, R^(D) is isopropyl or tolyl. In someembodiments, R^(D) is isopropyl.

In some embodiments, R^(D) is

In some embodiments, n is 1-2. In some embodiments, n is 1. In someembodiments, n is 2. In some embodiments, n is 3.

In some embodiments, X is a pseudohalide. In some embodiments, X is N₃or CN.

In some embodiments, X is halo. In some embodiments, X is F, Cl, or Br.In some embodiments, X is Cl or Br.

In some embodiments, R^(D) is

In some embodiments, p is 1-2. In some embodiments, p is 1, In someembodiments, p is 2. In some embodiments, p is 3.

In some embodiments, R⁴ and R⁵ are identical. In further embodiments, R⁴and R⁵ are aryl. In further embodiments, R⁴ and R⁵ are alkyl. In certainembodiments, R⁴ and R⁵ are tertiary alkyl. In further embodiments, R⁴and R⁵ are phenyl or methyl. In some embodiments, R⁴ and R⁵ are phenyl.

In some embodiments, R^(D) is

In further embodiments, n is 1. In further embodiments, n is 2. Infurther embodiments, n is 3.

In some embodiments, R^(x) is alkyl, aryl, aralkyl, or alkaryl. In someembodiments, R^(x) is alkyl or aryl. In some embodiments, R^(x) isaralkyl. In some embodiments, R^(x) is alkaryl.

In some embodiments R^(x) is alkyl. In some embodiments, R^(x) issubstituted alkyl. In some embodiments, R^(x) is substituted alkyl of 1to about 10 carbons. In some embodiments, R^(x) is substituted alkyl of1 to about 6 carbons. In some embodiments, R^(x) is substituted alkyl of1 to about 3 carbons. In some embodiments, R^(x) is unsubstituted alkyl.In some embodiments, R^(x) is unsubstituted alkyl of 1 to about 10carbons. In some embodiments, R^(x) is unsubstituted alkyl of 1 to about6 carbons. In some embodiments, R^(x) is unsubstituted alkyl of 1 toabout 3 carbons.

In some embodiments, R^(x) is aryl. In some embodiments, R^(x) issubstituted aryl. In some embodiments, R^(x) is substituted aryl of 6 toabout 12 carbons. In some embodiments, R^(x) is substituted aryl of 6 toabout 8 carbons. In some embodiments, R^(x) is unsubstituted aryl. Insome embodiments, R^(x) is unsubstituted aryl of 6 to about 12 carbons.In some embodiments, R^(x) is unsubstituted aryl of 6 to about 8carbons.

In some embodiments, m is 1. In some embodiments, m is 2. In someembodiments, m is 3.

In some embodiments, the polyolefin group has a molecular weight greaterthan 100 g/mol. In some embodiments, the polyolefin group has amolecular weight greater than 200 g/mol. In some embodiments, thepolyolefin group has a molecular weight greater than 400 g/mol. In someembodiments, the polyolefin group has a molecular weight greater than600 g/mol. In some embodiments, the polyolefin group has a molecularweight greater than 800 g/mol. In some embodiments, the polyolefin grouphas a molecular weight greater than 1000 g/mol. In some embodiments, thepolyolefin group has a molecular weight greater than 5000 g/mol. In someembodiments, the polyolefin group has a molecular weight greater than10,000 g/mol. In some embodiments, the polyolefin group has a molecularweight greater than 100,000 g/mol. In some embodiments, the polyolefingroup has a molecular weight greater than 500,000 g/mol. In someembodiments, the polyolefin group has a molecular weight greater than1,000,000 g/mol.

5. EXAMPLES

Certain embodiments provided herein are illustrated by the followingnon-limiting examples. Unless expressly stated to the contrary, alltemperatures and temperature ranges refer to the Centigrade system andthe term “room temperature” refers to about 20 to 25 degrees Celsius.

5.1 Examples 1-4

A four-neck 250 milliliter round-bottom flask was equipped with anoverhead mechanical stirrer and platinum resistance thermometer. Thisassembly was immersed into a heptane bath at −60° C. under dry nitrogengas in a substantially inert atmosphere glovebox. The flask was thencharged with the following reactants:

110 mL hexane equilibrated at −60° C.,

72 mL methylchloride equilibrated at −60° C.,

0.43 gram 2-chloro-2,4,4-trimethylpentane equilibrated at roomtemperature,

0.23 mL 2,6-dimethylpyridine equilibrated at room temperature, and

17 mL of isobutylene equilibrated at −60° C.

Then, the contents of the round-bottom flask were mixed and equilibratedat −60° C.

With continued stirring, next 3.1 mL titanium tetrachloride was chargedto the flask. The reaction was allowed to proceed 12 minutes and then 20mL of the polymerization solution was charged to 60 mL test tubes,equipped with threaded caps, immersed in the heptane bath maintained at−60° C.

The polymerization was allowed to continue in each test tube for 14additional minutes (26 total reaction minutes) at which point one of thetubes was terminated with 5 mL methanol to provide a comparative exampleprior to addition of a disulfide quencher. Immediately after completingthe comparative example, 0.090 g of furfurylmethyldisulfide was added toone of the tubes containing a reactive polymerization, while othersulfide quenching agents were added to 3 of the remaining test tubes.The furfurylmethyldisulfide quenching reaction (and other quenchingreactions) was allowed to proceed 15 minutes at which time 5 mL ofmethanol was charged to the tubes in order to terminate the quenchingreaction. A final polymerization test tube which contained no quencherwas then terminated with 5 g of methanol to provide a final comparativeexample (Control A). Non-quencher-containing reactions were used toprovide a comparative baseline for the quenching reactions and toprovide references for structural and molecular weight characterizationin the absence of a quenching agent.

The reactant quantities for Examples 1-4 and Control A are listed inTable I. Results are shown in Table V (infra).

TABLE I Example Disulfide Disulfide (g) 1 furfurylmethyldisulfide 0.0522 dimethyldisulfide 0.053 3 diethyldisulfide 0.068 4di-tert-butyldisulfide 0.100 Control A None 0

5.2 Examples 5-11

A four-neck 250 milliliter round-bottom flask was equipped with anoverhead mechanical stirrer and platinum resistance thermometer. Thisassembly was immersed into a heptane bath at −60° C. under dry nitrogengas in a substantially inert atmosphere glovebox. The flask was thencharged with the following reactants:

110 mL hexane equilibrated at −60° C.,

73.4 mL methylchloride equilibrated at −60° C.,

0.62 gram 2-chloro-2,4,4-trimethylpentane equilibrated at roomtemperature,

0.23 mL 2,6-dimethylpyridine equilibrated at room temperature, and

13.3 mL of isobutylene equilibrated at −60° C.

Then, the contents of the round-bottom flask were mixed and equilibratedat −60° C.

With continued stirring, next 2.28 mL titanium tetrachloride was chargedto the flask. The reaction was allowed to proceed 17 minutes and then1.32 mL diisopropyldisulfide was charged to the polymerization. Thesolution was immediately poured into 60 mL test tubes, equipped withthreaded caps, immersed in the heptane bath maintained at −60° C.

The quenching reaction was allowed to continue in each test tube for 10minutes at which point 0.80 mL methanol was charged to one of the tubes(example 5). Various terminators were charged to the remaining tubes asseparate examples (6-11).

The reactant quantities for Examples 5-11 are listed in Table II.Results are shown in Table V (infra).

TABLE II Example Terminator Terminator (g)  5 methanol 0.80  6 ethanol1.148  7 isopropanol 1.498  8 2-ethylhexanol 3.246  9 n-butylamine 1.82310 2-ethylhexylamine 1.91 11 tert-amylamine 2.172

5.3 Examples 12-16

A four-neck 250 milliliter round-bottom flask was equipped with anoverhead mechanical stirrer and platinum resistance thermometer. Thisassembly was immersed into a heptane bath at −60° C. under dry nitrogengas in a substantially inert atmosphere glovebox. The flask was thencharged with the following reactants:

72.6 mL hexane equilibrated at −60° C.,

48.4 mL methylchloride equilibrated at −60° C.,

3.43 gram 2-chloro-2,4,4-trimethylpentane equilibrated at roomtemperature,

0.23 mL 2,6-dimethylpyridine equilibrated at room temperature, and

73.6 mL of isobutylene equilibrated at −60° C.

Then, the contents of the round-bottom flask were mixed and equilibratedat −60° C.

With continued stirring, next 1.27 mL titanium tetrachloride was chargedto the flask. The reaction was allowed to proceed 27 minutes and then4.05 mL diisopropyldisulfide was charged to the polymerization followedby immediate addition of 4.3 mL titanium tetrachloride. The solution wasimmediately poured into 60 mL test tubes, equipped with threaded caps,immersed in the heptane bath maintained at −60° C.

The quenching reaction was allowed to continue in each test tube for 16minutes at which point 2.807 g ethanol was charged to one of the tubes(example 12). Various terminators were charged to the remaining tubes asseparate examples (13-16).

The reactant quantities for Examples 12-16 are listed in Table III.Results are shown in Table V (infra).

TABLE III Example Terminator Terminator (g) 12 ethanol 2.807 13sec-butanol 4.516 14 isopropanol 3.661 15 ethanethiol 3.785 16n-propanethiol 4.640

5.4 Examples 17-21

A four-neck 250 milliliter round-bottom flask was equipped with anoverhead mechanical stirrer and platinum resistance thermometer. Thisassembly was immersed into a heptane bath at −60° C. under dry nitrogengas in a substantially inert atmosphere glovebox. The flask was thencharged with the following reactants:

110 mL hexane equilibrated at −60° C.,

73.4 mL methylchloride equilibrated at −60° C.,

0.62 gram 2-chloro-2,4,4-trimethylpentane equilibrated at roomtemperature,

0.23 mL 2,6-dimethylpyridine equilibrated at room temperature, and

13.3 mL of isobutylene equilibrated at −60° C.

Then, the contents of the round-bottom flask were mixed and equilibratedat −60° C.

With continued stirring, next 2.28 mL titanium tetrachloride was chargedto the flask. The reaction was allowed to proceed 18 minutes and then1.89 mL ditolyldisulfide was charged to the polymerization. The solutionwas immediately poured into 60 mL test tubes, equipped with threadedcaps, immersed in the heptane bath maintained at −60° C.

The quenching reaction was allowed to continue in each test tube for 16minutes at which point 1.40 g methanol was charged to one of the tubes(example 17). Various terminators were charged to the remaining tubes asseparate examples (18-21). A final polymerization test tube whichcontained no quencher was then terminated with 5 g of methanol toprovide a final comparative example (Control B). Non-quencher-containingreactions were used to provide a comparative baseline for the quenchingreactions and to provide references for structural and molecular weightcharacterization in the absence of a quenching agent.

The reactant quantities for Examples 17-21 and Comparative B are listedin Table IV. Results are shown in Table V (infra).

TABLE IV Example Terminator Terminator (g) 17 methanol 1.40 18isopropanol 2.62 19 n-butylamine 3.19 20 triethylamine 4.41 21n-propanethiol 3.32 B methanol 5.0

5.5 Example 22

A four-neck 1000 milliliter round-bottom flask was equipped with anoverhead mechanical stirrer and platinum resistance thermometer. Thisassembly was immersed into a heptane bath at −60° C. under dry nitrogengas in a substantially inert atmosphere glovebox. The flask was thencharged with the following reactants:

189 mL hexane equilibrated at −60° C.,

216 mL methylchloride equilibrated at −60° C.,

6.25 gram 2-chloro-2,4,4-trimethylpentane equilibrated at roomtemperature,

0.48 mL 2,6-dimethylpyridine equilibrated at room temperature, and

135 mL of isobutylene equilibrated at −60° C.

Then, the contents of the round-bottom flask were mixed and equilibratedat −60° C.

With continued stirring, next 2.03 mL titanium tetrachloride was chargedto the flask to initiate the isobutylene polymerization. Thepolymerization was allowed to proceed 90 minutes and then 14.13 gdibromoethyldisulfide was charged to the polymerization. Immediatelyafter the quencher addition, 30.24 mL titanium tetrachloride was chargedto the reaction mixture and the solution was allowed to react 22minutes. The reaction was then terminated by addition of 29.3 mLtriethylamine equilibrated at −60° C. The solution was stirred for 10minutes and then 73.2 mL methanol equilibrated at −60° C. was charged toreaction slowly. The solution was removed from the glove box andvolatile components were evaporated under ambient conditions. Thehexane/polyisobutylene layer was washed with a 5% aqueous HCl solutionand then deionized H₂O until extracts were neutral. The wet organicphase was dried over MgSO₄, filtered, and concentrated on aroto-evaporator. Results are shown in Table V (infra).

5.6 Example 23

A four-neck 1000 milliliter round-bottom flask was equipped with anoverhead mechanical stirrer and platinum resistance thermometer. Thisassembly was immersed into a heptane bath at −60° C. under dry nitrogengas in a substantially inert atmosphere glovebox. The flask was thencharged with the following reactants:

169 mL hexane equilibrated at −60° C.,

156 mL methylchloride equilibrated at −60° C.,

5.41 gram 2-chloro-2,4,4-trimethylpentane equilibrated at roomtemperature,

0.35 mL 2,6-dimethylpyridine equilibrated at room temperature, and

65.4 mL of isobutylene equilibrated at −60° C.

Then, the contents of the round-bottom flask were mixed and equilibratedat −60° C.

With continued stirring, 1.44 mL titanium tetrachloride was charged tothe flask to initiate the isobutylene polymerization. The polymerizationwas allowed to proceed 60 minutes and then 8.34 g dichloroethyldisulfidewas charged to the polymerization. Immediately after the quencheraddition, 34.5 mL titanium tetrachloride was charged to the reactionmixture and the solution was allowed to react 10 minutes. The reactionwas then terminated by addition of 30.4 mL triethylamine equilibrated at−60° C. The solution was stirred for 10 minutes and then 81 mL methanolequilibrated at −60° C. was charged to reaction slowly. The solution wasremoved from the glove box and volatile components were evaporated underambient conditions. The hexane/polyisobutylene layer was washed with a5% aqueous HCl solution and then deionized H₂O until extracts wereneutral. The wet organic phase was dried over MgSO₄, filtered, andconcentrated on a roto-evaporator. Results are shown in Table V (infra).

5.7 Example 24

A four-neck 250 milliliter round-bottom flask was equipped with anoverhead mechanical stirrer and platinum resistance thermometer. Thisassembly was immersed into a heptane bath at −60° C. under dry nitrogengas in a substantially inert atmosphere glovebox. The flask was thencharged with the following reactants:

110 mL hexane equilibrated at −60° C.,

73 mL methylchloride equilibrated at −60° C.,

0.62 gram 2-chloro-2,4,4-trimethylpentane equilibrated at roomtemperature,

0.23 mL 2,6-dimethylpyridine equilibrated at room temperature, and

13.3 mL of isobutylene equilibrated at −60° C.

Then, the contents of the round-bottom flask were mixed and equilibratedat −60° C.

With continued stirring, 2.28 mL titanium tetrachloride was charged tothe flask to initiate the isobutylene polymerization. The polymerizationwas allowed to proceed 17 minutes and then 3.15 gtert-butyldiphenylsiloxyethyldisulfide was charged to the polymerizationand allowed to react 15 minutes. The reaction was then terminated byaddition of 18.4 mL dibutylamine. The solution was removed from theglove box and volatile components were evaporated under ambientconditions. The hexane/PIB layer was washed with a 5% aqueous HClsolution and then deionized H₂O until extracts were neutral. The wetorganic phase was dried over MgSO₄, filtered, and concentrated on aroto-evaporator. Results are shown in Table V (infra).

5.8 Procedure for Collecting ¹H NMR Data

¹H NMR spectra were collected using a Varian (300 MHz) spectrophotometerusing samples concentrations of 3 percent to 5 percent (weight/weight)in CDCl₃. ¹H NMR spectra were used for analysis of the end groups.Fractions of exo-olefin, endo-olefin, tert-chloride, coupled olefin, andsulfide (PIBthioether) chain ends were obtained using ¹H NMR integrationas described in the following section.

5.8.1 Procedure for Calculating the Fractional Amounts of Chain Ends onthe Polyisobutylene Product

The fractions of exo-olefin, endo-olefin, sulfide (PIBthioether),tert-chloride chain ends, and coupled products in the polyisobutylenesamples were quantified using ¹H NMR integration. In some instancescoupled products were deemed to be absent by qualitative inspection ofthe ¹H NMR spectrum, and by confirming the absence of a shoulder on thelow elution volume side of the main polymer peak in the Gel PermeationChromatography chromatogram.

The fractional molar amount of each type of chain end was obtained usingan equation analogous to the equation given below for determining thefractional amount of exo-olefin,F(exo)=(A _(exo))/(A _(exo) +A _(endo) +A _(tert-Cl) +A _(sulfide)+2A_(coupled))  (1)where A_(endo) is the area of the single olefinic resonance at 5.15 ppm,A_(exo) is the area of the exo-olefinic resonance 4.63 ppm, andA_(tert-Cl) was calculated as follows:A _(tert-Cl)=(A _(1.65-1.72)/6)−A _(endo)  (2)orA _(tert-Cl)=(A _(1.95)/2)where A_(1.65-1.72) is the integrated area of the convoluted peaksassociated with the gem-dimethyl protons of the endo-olefin and thetert-chloride chain ends and A_(1.95) is the integrated area of the peakassociated with methylene protons on the end of the polyisobutene chain.In some cases, sulfide terminated PIB yielded peaks in the area between1.65 and 1.72, which made it very difficult to accurately measure thearea associated with only the tert-Cl chain ends; therefore, in thosecases, we utilized the peak at 1.95 for quantification of tert-Cl chainends. It will be noted that a co-efficient of 2 appears in equation (1)for coupled product, to account for the fact that creation of theseproducts consumes 2 polyisobutylene chains. A_(coupled) was calculatedas follows:A _(coupled)=(A _(5.0-4.75) −A _(4.5-4.75))/2  (3)where A_(5.0-4.75) is the integrated area of the convoluted peaksassociated with one of the exo-olefin protons and the two identicalprotons of the coupled product, and where A_(4.5-4.75) is the integratedarea of the peak associated with the other exo-olefin proton.

The integrated area and fractional amount of sulfide terminated PIB wereobtained on a product-specific basis. Typically, a well-resolved peakassociated with the proton(s) of the non-polyisobutenyl residue of thethioether chain end was integrated. For example, in Example 9 of thepresent invention, the area associated with the singe proton of theisopropyl group (multiplet at 2.93 ppm) attached to sulfur on the PIBchain end was integrated in order to quantify the amount of sulfidechain ends in the composition (see figure below).

5.9 Results

The results for all examples described, supra, are summarized in TableV.

TABLE V Molar Composition of Chain Ends after Quenching ReactionSulfide- Vinylidene Endo terminated terminated Olefin Tert-Cl CoupledPolyolefin Ex Disulfide Terminator (mole %) (mole %) (mole %) (mole %)(mole %) Other 1 Furfuryl- Methanol 22 2 2 0 74 0 methyl 2 DimethylMethanol 23 1 1 0 75 0 3 Diethyl Methanol 40 2 1 2 55 0 4 di-tert-butylMethanol 69 1 15 15 0 0 A None Methanol 4 1 94 1 0 0 5 DiisopropylMethanol 78.6 4.4 8.9 0.5 0.0 7.6 6 Diisopropyl Ethanol 77.7 4.3 16.21.7 0.0 0.1 7 Diisopropyl Isopropanol 84.3 3.5 11.5 0.6 0.0 0.1 8Diisopropyl 2-ethylhexanol 86.5 5.8 7.6 0.1 0.0 0.0 9 Diisopropyln-butylamine 10.3 0.0 0.0 0.8 88.9 0 10 Diisopropyl 2-ethylhexylamine10.0 0.9 0.9 0.5 87.7 0 11 Diisopropyl Tert-amylamine 10.3 0.0 0.0 0.888.9 0 12 Diisopropyl Ethanol 80.5 5.2 14.0 0.4 0.0 0 13 Diisopropylsec-butanol 82.5 5.1 11.8 0.6 0.0 0 14 Diisopropyl Isopropanol 82.8 6.110.3 0.7 0.0 0.1 15 Diisopropyl ethanethiol 3.6 2.2 22.4 0.0 71.8 0 16Diisopropyl n-propanethiol 3.5 0.3 13.0 0.0 83.2 0 17 Ditolyl Methanol11.8 1.5 39.1 0.0 29.5 18.1 18 Ditolyl Isopropanol 29.9 2.0 6.9 0.0 38.522.7 19 Ditolyl n-butylamine 9.0 0.9 4.7 0.0 81.3 4.1 20 Ditolyltriethylamine 14.6 0.0 0.0 0.0 85.4 0 21 Ditolyl n-propanethiol 0.0 0.01.6 0.0 86.0 12.4 B None Methanol 2.0 0.4 97.6 0.0 0.0 0.0 22Dibromo-ethyl Triethylamine 3 0 0 0 97 0 23 Dichloro-ethyl Triethylamine3 0 0 0 97 0 24 Di-tert- dibutylamine 11 0 0 3 86 0 butyldiphenylsiloxyethyl

In example 15, the 71.8% total sulfide-terminated polyolefin product isa mixture of 73 mole percent isopropylsulfide-terminated product and 27mole percent ethylsulfide-terminated product.

In example 16, the sulfide-terminated polyolefin product is 100 molepercent n-propylsulfide-terminated product.

In example 21, the sulfide-terminated polyolefin product is 100 molepercent tolylsulfide-terminated product.

The embodiments and examples described above are intended to be merelyexemplary, and such examples and embodiments are non-limiting. One ofordinary skill in the art will recognize, or will be able to ascertainusing no more than routine experimentation, modifications of theembodiments and examples described herein. Such modifications areconsidered to be within the scope of the claimed subject matter and areencompassed by the appended claims.

1. A compound of formula VIII:

wherein R¹ is a polyolefin group; R^(D) is alkyl of 1 to 7 carbons, substituted alkyl of at least 3 carbons, unsubstituted aryl, alkaryl, aralkyl,

wherein m is 1-3; n is 1-3; p is 1-3; X is halo or a pseudohalide; R³ is tert-butyl; R⁴ and R⁵ are each, independently, aryl or alkyl; and R^(x) is hydrocarbyl.
 2. The compound of claim 1, wherein R^(D) is alkyl of 1 to 7 carbons or substituted alkyl of at least 3 carbons.
 3. The compound of claim 1, wherein R^(D) is alkaryl.
 4. The compound of claim 1, wherein R^(D) is methyl, ethyl, tert-butyl, isopropyl, or tolyl.
 5. The compound of claim 1, wherein R^(D) is

and n is
 2. 6. The compound of claim 1, wherein R^(D) is

p is 2, and R³ is tert-butyl.
 7. The compound of claim 1, wherein the polyolefin group has a molecular weight greater than 200 g/mol.
 8. The compound of claim 1, wherein R¹ is a polyisobutylene group. 